Objective: To determine the thermal stability of polyvinyl alcohol films under different concentrations of CeO2 nanoceria. Method: Cerium Oxide doped polyvinyl alcohol (PVA) nano-composites were synthesized by the traditional solution casting method for various concentrations of nano CeO2 by solution combustion method. The thermal properties of prepared PVA-2.5 wt% CeO2, PVA-7.5 wt% CeO2 , PVA-12.5 wt% CeO2, and PVA-25 wt% CeO2 composite films were elucidated by using techniques such as Differential Scanning Calorimetry, Thermogravimetry analysis and Differential Thermal analysis. Findings: The glass transition temperature of the pure PVA is found to be 114°C, whereas it varies between 110°C-120°C for composite films. The melting temperature of the composite films is the same as that of pure PVA except in the case of 7.5wt% CeO2 and 25wt% CeO2 composites. The reduced melting point of these composites elicits a decrease in crystallinity. A 12.5 wt % and 25 wt% CeO2-PVA nano-composite films exhibit an increase in the final degradation temperature, a high specific heat capacity, low mass loss, and a larger residual weight, indicating their potential applicability in thermal coating and thermal sensing applications. Polyvinyl alcohol (PVA) films are being used routinely as a dielectric layer for electrical applications due to the good physiochemical and dialectic properties of the material. An incorporation of CeO2 nanoceria improves not only the thermal but also the mechanical properties of PVA and extends its application for electrical and optical operation. Here in the present study, different concentrations of CeO2 were incorporated with the PVA and analysed for the thermal properties. The study showed that 12.5 wt % and 25 wt% CeO2-PVA nano-composite enhanced PVA film thermal stability. Keywords: PVA-CeO2 Nanocomposites; Differential Scanning Calorimetry; Thermogravimetry Analysis and Differential Thermal Analysis; Physical properties and thermal properties